Insecticide



Patented May 16, 1944 UNITED STATES PATENTVVOFFICE msnc'rromn Julius Hyman, Chicago, Ill., assignor to Vclslcol Corporation, Chicago, 111., a corporation of Illimiu activity, inasmuch as, for example, 2,6"

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No Drawing. Application January 29, 1943, Serial No. 473,961

11 Claims. (Cl. 167-30) Thisinvention relates to novel insecticides and dimethyl-l,4-naphthoquinone having the folparticularly to a class of compounds found to lowing structural formula: possess insecticidal potency of a comparatively high order and useful'in relatively small proportion in the preparation oi. compositions of a toxic 5 and repellant nature to a great variety of insects and allied forms of life.

More specifically my invention relates to the a use of one or more methylated 1,4-naphthoquinones as an active ingredient in an insecticidal l composition, which may include a solubilizing mah :3 5;'g gfiii gz i gggggggggfi terial therefor and a conventional carrier or base, g; to that of rowitamm K itself and wherein the methylated 1,4-naphthoquinone the other g while may be the prime active ingredient or may be in thoqumone oxide d 2 methy1 1 additive or synergistic association with other maiii are quinone diacetate, having respectively the foltcrials having greater or lesser insecticidal polowin Structural formulas. tency. The methylated 1,4 naphthoquinones a g which I have found useful as aforesaid, and as hereinafter more fully set forth, have the following structural formula:

R II R coon R R are both said to show high vitamin K activity,

R they have been found to possess insecticidal po- 6 tency of only a comparatively low order. It will therefore be understood that the compounds g g? 2 .3 2? fi zsgg gg fgsg 2 3 which I have found to possess insecticidal pomethyl group A typical example of such a tency of a comparatively high order, and whose pound is 2 methy1 lfimaphthoqumone, known use is contemplated hereimwhile structurally re- 53 prouvitamin K, possesses t following lated. to Compounds of activity are not structure: necessarily related in the degree of their respective potency or activity. I preferablyuse the methylated lA-naphthoquinones by dissolving them prior to use in a suitable-solvent or solvents, such as for example pine oil, a higher boiling chlorinated hydrocarbon oil, or a hydrocarbon oil rich in mono- 4c and di-methyl naphthalenes (known to the trade as Velsicol AR-50) or rich in di and tri-methyl Th se naphth q a yellow crystalline naphthalenes (known to the trade as Velslcol M and are most re y P pared by the ac- AR-fiil). I preferably use the latter hydrocartion. of chromic oxide (C10 3) on methylated naphhon oils which are rich in methylabed nanthat cm n acetic ac d S t onn akin t lenes by reason of the fact that they not only Lt-naphthoquinones, iii is 11686838 that the 1,4 are gggd golubluzmg agents but they are also ac- Pwmom Q the Original methylated naphtha" tive per se as insecticidal ingredients, as set forth lene be unsubstituted. The manufacture of 2- m my (go-pending applicaflcn serial 444,397 et wl L -n u thcqu one has ee e c i d In View or the fact that the contemplated peated y in t e pr or t a d literature. and so napththoquinones are tat slightly soluble in the the homologous naphthoquinones may be proconventional petroleum or kerosene insecticide duced. srly, with satisfactory yields. bases, use is made of the foregoing or similar The insecticidal value of these compounds does agents which are mutual solvents when such not however appear to be related to their vitabases are used in forming the insecticidal comsiticn.

As an example of the action of methylated 1,4

naphthoquinones toward flies when tested by the Feet-Grady method, a mixture comprising 1% oi 2-methyl-1,4-naphthoquinone (pro-vitamin K), 25% of Velsicol ARI-50 and 74% of a socalled odorless petroleum insecticide base (Sonneborns Dec-Base) or deodorized kerosene gave a 90% knock-down in 7 V2 minutes and a 24 hour mortality of 91%. Under the same conditions the Oilicial Test Insecticide showed a 24 hour mortality of 48%. thus giving the aforementioned insecticidal naphthoquinone composition a Peet- Grady rating of +43.

Under the same conditions a mixture such as the above, but in which the pro-vitamin K had been replaced by 1,4-naphthoquinone showed a 90% knock-down time of over 10 minutes and a Feet-Grady mortality rating of +6. Like substitution oi 1,2-naphthoquinone also showed poor knock-down and gave a Peet-Grady rating of As indicative of the high potency of the 2-methyl-l,4-naphthoquinone per se used in the first example, a check-run in which 25% of Velsicol Aft-50 and 75% of Dec-Base only was used showed a slow knock-down and a Pest-Grady rating of 27.

When solutions comprising 3% oil z-methyl- 1,4-naphthoquinone, 25% of Art-50 and 72% o! Dec-Base were tested on German roaches (adult females) by means of a micro-syringe, it was found that 0.005 cc. per roach was suflicient to kill 40% of the roaches in 24 hours. Where 2,6- dimethyl- 1,4-naphthoquinone was used in place of the pro-vitamin K, the same dosage produced a 90% mortality. On the other hand, the Oflicial Test Insecticide distributed by the National Association oi Insecticide and Disinfectant Manuiacturers, Inc., showed a 20% mortalityunder similar conditions. The O. '1. I. produced its usual rapid paralysis, but there was high recovery in this treatment.

I have also found that methylated 1,4-naphthoquinone insecticidal compositions appear to be quite toxic to agricultural pests. For example.

a solution was made containing 80% by weight of Velsicol Alt-60 and by weight 0! 2-methyl- 1,4-naphthoquinone. when 5% of this solution was mixed with 95% of pyrophyllite dust, the resulting mixture appeared to give good protection against Colorado potato beetle larvae, although the protection was not as good as that aflorded by an equal quantity oi! derris resinate, assaying rotenone. No foliage damage was observed.

I claim as my invention:

1. An insecticidal composition containing as an active ingredient 2,6-dimethyl-L4-naphthoquinone dissolved in a solvent.

2. Aninsecticidal composition containing as an active ingredient z-methyl-ls-naphthoquinone dissolved in a solvent.-

3. An insecticidal composition containing as an active ingredient a methylated 1,4-naphthoquinone dissolved in a solvent.

4. An insecticidal composition containing as an active ingredient a methylated 1,4-naphthoquinone dissolved in a petroleum insecticide base by means of a mutual solvent."

5. An insecticidal composition containing as an active ingredient a methylated 1,4-napthoquinone dissolved in a petroleum insecticide base by means of a mutual solvent composed of a hydrocarbon oil rich in methylated naphthalene.

8. An insecticidal composition containing a methylated 1,4-naphthoquinone together with an inert dust.

'1. An insecticidal composition containing a methylated 1.4-naphthoquinone dissolved in a solvent and extended therewith over an agricultural dust.

8. An insecticidal composition containing as an' active in edient 2-methyl-L4-naphthoquinone dissolved of a mutual solvent.

9. An insecticidal composition containing as an active ingredient z-methyl-lA-naphthoquintme dissolved in a petroleum insecticide base by means of a mutual solvent composed of a hydrocarbon oil rich in methylated naphthalene.

10. An insecticidal composition containing 2- methyl-1,4-naphthoquinone together with an inert dust.

11. An insecticidal composition containing 2- methyl-1,4-naphthoquinone dissolved in a solvent and extended therewith over an agricultural dust.

' JULIUS I-IYMAN.

a petroleum insecticide base by means 

